LIPON COATINGS FOR HIGH VOLTAGE AND HIGH TEMPERATURE Li-ION BATTERY CATHODES

ABSTRACT

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with government support under contract No. DE-AC05-00OR22725 awarded by the U.S. Department of Energy. The government has certain rights in this invention.

FIELD OF THE INVENTION

This invention relates generally to lithium batteries, and more particularly to protective coatings for cathode materials.

BACKGROUND OF THE INVENTION

Improved energy density for rechargeable Li-ion batteries requires use of high-capacity and high-voltage cathode materials, but charging to voltages approaching 4.5-5V invariably causes rapid loss of capacity with cycling. This degradation is attributed to several mechanisms, including oxygen loss, transition metal dissolution, lattice or particle instability, or reactions with the electrolyte or impurities. One promising solution is to coat the cathode particle surface with a protective material, such as a metal oxide. At this time, it remains unclear why such metal oxide coatings improve the high-voltage cycling behavior and whether film uniformity is critical.

Generally coatings for cathode materials are stable compounds that do not contain lithium, such as AlPO₄, ZrO₂, Al₂O₃, ZnO, and Bi₂O₃. Coatings are typically applied to cathode powders by solution or sot gel coating. These materials then need to be heat treated at elevated temperature to decompose the precursor and form the oxide coating. The amount and morphology of the coating is not well characterized. In some cases the coating is clearly not uniform. In many cases, the coating adds substantially to the mass.

SUMMARY OF THE INVENTION

A lithium ion battery includes an anode and a cathode. The cathode comprises a lithium, manganese, nickel, and oxygen containing compound. A liquid electrolyte layer exits between the anode and the cathode to facilitate ion-transport. A protective layer is deposited between the cathode and the electrolyte. The protective layer comprises lithium phosphorus oxynitride.

The electrolyte can be free of lithium phosphorus oxynitride. The cathode can comprise Li[Ni_(x)Mn_(2-x)]O₄, where x is 0.5±0.1.

The cathode can also comprise a lithium, manganese, oxygen, nickel and cobalt containing compound. The lithium, manganese, oxygen, nickel and cobalt containing compound can comprise Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1. Alternatively, the cathode composition can also be described in terms of layered-layered composite formula given by the general formula xLi₂MnO₃.(1-x)LiMO₂, where M=Mn, Co, Ni and x can range from 0.2-0.7. The lithium, manganese, oxygen, nickel and cobalt containing compound cathode compound can comprise Li_(1.2)Mn_(0.525)Ni_(0.175)Co_(0.1)O₂. The cathode can also comprise a solid solution of Li_(1+x)Mn_(2-y)O₄, where x and y are independently 0 to 0.2, and Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1.

The lithium phosphorus oxynitride protective layer can be from 0.5 nm to 1 μm thick.

The lithium phosphorus oxynitride protective layer can be vapor deposited on the lithium, manganese, nickel, and oxygen containing compound. The lithium, manganese, nickel, and oxygen containing compound can be provided as particles, and the protective layer can be vapor deposited on the exterior surface and surface accessible pores of the particles. The particles can have a diameter of between 10 nm and 50 μm, or between 100 nm and 15 μm.

The lithium, manganese, nickel, and oxygen containing compound can further comprise at least one dopant which enhances electronic transport in the protective layer. The dopant can be at least one selected from the group consisting of transition metal elements, such as Ti, Fe, Ni, V, Cr, Cu, and Co. The dopant can be provided at a concentration of between 1% to 100% of the P mole content, or in another aspect from 25%-50% of the P content by moles.

A method of making a cathode for a lithium ion battery can include the step of providing a cathode material comprising a lithium, manganese, nickel and oxygen containing compound. A lithium phosphate target is also provided. The lithium phosphate is sputtered in a nitrogen plasma to coat the lithium, manganese, nickel and oxygen containing compound with at least a 0.5 nm coating of lithium phosphorus oxynitride.

The sputtering step can be RF magnetron sputtering. The cathode material can be provided as particles. The method can further comprise the step of agitating, stirring, vibrating, or flowing the particles during the sputtering step.

The method can further comprise the step of applying a lithium salt electrolyte layer in operable contact with the cathode. The electrolyte layer can be free of lithium phosphorus oxynitride. The method can further comprise the step of applying an anode layer in operable contact with the electrolyte layer.

A lithium ion battery includes an anode, a cathode, and an electrolyte disposed between the anode and the cathode. A protective layer is disposed between the cathode and the electrolyte. The protective layer comprises lithium phosphorus oxynitride and at least one electronic transport enhancing dopant. The dopant can be at least one selected from the group consisting of Ti, Fe, Ni, V, Cr, Cu, and Co. The dopant can be provided at a concentration of from 1% to 100% of the P mole content, and in another embodiment can be provided at a concentration of from 25% to 50% of the P content by moles. The cathode can comprise a lithium, manganese, nickel and oxygen containing compound.

A method of operating a battery includes the steps of providing a lithium ion battery comprising an anode, a cathode, and an electrolyte layer between the anode and the cathode. The cathode comprises a lithium, manganese, nickel, and oxygen containing compound. The electrolyte can be free of lithium phosphorus oxynitride. A protective layer is sandwiched or deposited between the cathode layer and the electrolyte. The protective layer comprises lithium phosphorus oxynitride. The method further includes the step of operating the battery at elevated operating conditions comprising at least one selected from the group consisting of a temperature of at least 50° C. and a voltage of at least 4.5 V. The battery can be operated at a temperature of between 50° C. and 80° C. The battery can be operated at a voltage of between 4.5 V and 5.4 V.

A method of operating a battery includes the steps of providing a lithium ion battery comprising an anode, a cathode, and an electrolyte disposed between the anode and the cathode. The electrolyte can be free of lithium phosphorus oxynitride. A protective layer is deposited between the cathode layer and the electrolyte. The protective layer comprises lithium phosphorus oxynitride and at least one electronic transport enhancing dopant. The method further includes the step of operating the battery at elevated operating conditions comprising at least one selected from the group consisting of a temperature of at least 50° C. and a voltage of at least 4.5 V. The battery can be operated at a temperature of between 50° C. and 80° C. The battery can be operated at a voltage of between 4.5 V and 5.4 V. The dopant can be at least one selected from the group consisting of Ti, Fe, Ni, V, Cr, Cu, and Co. The dopant can be provided at a concentration of from 1% to 100% of the P mole content, and in another embodiment can be provided at a concentration of from 25% to 50% of the P content by moles. The cathode can comprise a lithium, manganese, nickel and oxygen containing compound.

BRIEF DESCRIPTION OF THE DRAWINGS

There are shown in the drawings embodiments that are presently preferred it being understood that the invention is not limited to the arrangements and instrumentalities shown, wherein:

FIG. 1 is a plot of discharge capacity (mAh/g) with cycle number.

FIG. 2 is a plot of discharge potential (V) vs. capacity (mAh/g) for Lipon-coated MNO cycled at room temperature.

FIG. 3 is a plot of discharge potential (V) vs. capacity (mAh/g) for bare MNO cycled at room temperature.

FIG. 4 is a plot of discharge potential (V) vs. capacity (mAh/g) for Lipon-coated MNO cycled at 60° C.

FIG. 5 is a plot of discharge potential (V) vs. capacity (mAh/g) for bare MNO cycled at 60° C.

FIG. 6 is a plot of discharge capacity vs. cycle number at various C-rates, cycled at 25° C.

FIG. 7 is a plot of capacity (mAh/g) vs. cycle number for Lipon coated Li-rich MNC at differing C-rates.

FIG. 8 is a plot of voltage (V) vs. Li/Li⁺ vs. capacity (mAh/g) at different C-rates.

FIG. 9 is a plot of capacity (mAh/g) vs. rates of discharge for 1h-Lipon coated Li-rich NMC and 3h-Lipon coated Li-rich NMC.

FIG. 10 is a plot of capacity (mAh/g) vs. rates of discharge/C rate for Lipon coated Li-rich NMC and convention

FIG. 11 is a plot of voltage (V) vs. Li/Li⁺ vs capacity (mAh/g) for Lipon-coated NMC for a 1^(st) cycle charge and a first cycle discharge.

FIG. 12 is a scanning electron micrograph (SEM) of uncoated LiMn_(1.5)Ni_(0.5)O₄.

FIG. 13 is an SEM of Lipon-coated LiMn_(1.5)Ni_(0.5)O₄ after a 0.5 hr deposition.

FIG. 14 is an SEM of Fe-Lipon-coated LiMn_(1.5)Ni_(0.5)O₄ after a 2 hr deposition.

FIG. 15 is an SEM of Ti-Lipon-coated LiMn_(1.5)Ni_(0.5)O₄ after a 2 hr deposition.

FIG. 16 is a plot of discharge capacity (mAh/g) vs. cycle number for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at room temperature.

FIG. 17 is a plot of potential (V) vs. capacity (mAh/g) for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at room temperature.

FIG. 18 is a plot of discharge capacity (mAh/g) vs. cycle number for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at 60° C.

FIG. 19 is a plot of potential (V) vs. capacity (mAh/g) for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at 60° C.

DETAILED DESCRIPTION OF THE INVENTION

A lithium ion battery includes an anode and a cathode. The cathode comprises a lithium, manganese, nickel, and oxygen (LMNO) containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is disposed between the cathode and the electrolyte. The protective layer comprises lithium phosphorus oxynitride (Lipon). Lipon is an amorphous coating, free of grain boundaries. This material contains lithium, conducts lithium ions, and does not consume lithium as the battery is cycled.

A thin Lipon coating applied to a Li-ion battery cathode acts to stabilize the interface when cycled in a battery with a liquid organic liquid electrolyte, thus providing for an enhanced cycle life with less capacity fade. This is particularly important for cathodes cycled to higher voltage and higher temperatures. Dissolution and degradation processes are accelerated at higher temperatures and higher voltages. The Lipon may also slow the gradual increase in the internal resistance of the cell which gradually limits the power performance of the battery.

There is a large improvement for Lipon on LMNO cathodes such as Li(Ni_(0.5)Mn_(1.5))O₄ cathodes cycled to high voltage at high temperature. The LiMn_(1.5)Ni_(0.5)O₄(MNO) spine) cathode has a high voltage plateau ˜4.7V, comprises non-toxic elements, and utilizes Mn which is much less expensive than Co in LiCoO₂.

The electrolyte can be free of lithium phosphorus oxynitride. The cathode can comprise Li[Ni_(x)Mn_(2-x)]O₄, where x is 0.5±0.1. The cathode compound can comprise LiMn_(1.5)Ni_(0.5)O₄. The cathode compound can xLi₂MnO₃.(1-x)LiMO₂, where M=Mn, Co, Ni and x can range from 0.2-0.7.

The cathode can comprise a lithium, manganese, oxygen, nickel and cobalt containing compound (NMC and sometimes MNC). The lithium, manganese, oxygen, nickel and cobalt containing compound can comprise Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1. The lithium, manganese, oxygen, nickel and cobalt containing compound cathode compound can comprise Li_(1.2)Mn_(0.525)Ni_(0.175)Co_(0.1)O₂. This cathode is more generally known as a solid solution of Li[Li_(1/3)Mn_(2/3)]O₂+Li[Mn_(0.3)Ni_(0.45)Co_(0.25)]O₂. The cathode can comprise a solid solution of Li_(1+x)Mn_(2-y)O₄, where x and y are independently 0 to 0.2, and Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1.

The lithium phosphorus oxynitride protective layer can be from 0.5 nm to 1 μm thick. At the low end, this represents a small additional mass to battery, <0.5%. The lithium phosphorus oxynitride protective layer can be from 0.5 nm to 10 nm thick.

The lithium phosphorus oxynitride protective layer can be vapor deposited on the lithium, manganese, nickel, and oxygen containing compound. The lithium, manganese, nickel, and oxygen containing compound can be provided as particles, and the protective layer can be vapor deposited on the exterior surface and surface accessible pores of the particles. The particles can have a diameter of between 100 nm and 15 μm, or between 10 nm and 50 μm.

Lipon coatings do not need to coat the full surface area of the cathode powders to be effective. Some cathode powders are quite porous and have a high surface area. It is unlikely that Lipon coats all of the surface area. The morphology of the coating is continuous with uniform thickness. The coating is conformal if the cathode surface is smooth and fully accessible to the vapor source.

Fabrication of the Cathode

A method of making a cathode for a lithium ion battery can include the step of providing a cathode material comprising a lithium, manganese, nickel and oxygen containing compound. A lithium phosphate target is also provided. The lithium phosphate is sputtered in a nitrogen plasma to coat the lithium, manganese, nickel and oxygen containing compound with at least a 1 nm coating of lithium phosphorus oxynitride.

The sputtering step can be RF magnetron sputtering. The cathode material can be provided as particles. The method can further comprise the step of agitating or flowing the particles during the sputtering step. The advantages of RF-magnetron sputtering include the absence of a need for drying, the application of smooth ˜1 nm coatings are possible, no heat treatment is necessary, and it is a clean material process compared to solution-based approaches. There is also less material wasting compared to solution-based coating techniques. However, other application methods are possible and are within the scope of the invention.

Lipon is deposited by RF magnetron sputtering in a N₂ plasma at ambient temperature. This is a one step process. Lipon is deposited onto free flowing cathode powders, with sufficient stirring or tumbling of the powders during deposition for a uniform coating. In this case, the powder is then mixed with a binder and conductive additives to make a slurry, cast onto a metal foil current collector, dried, and finally pressed or calendared to make a typical battery electrode. Alternatively, Lipon can be deposited onto a prefabricated coating of the cathode material, which includes the cathode particles plus a binder plus other additives coated onto a metal foil current collector.

Assembly of the Li Battery

Any suitable electrolyte can be used. Suitable electrolytes include salts of lithium, including LiPF₆, LiClO₄, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(oxatlato)borate (LiBOB), dissolved in pure or mixtures of organic solvents, including linear and cyclic carbonates such a propylene carbonate, dimethyl carbonate, and others. A possible electrolyte is LiPF₆ dissolved in a mixture of organic carbonates including ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, or others. Other electrolytes might include alternative dissolved Li salts and solvents.

The method can further comprise the step of applying a lithium salt electrolyte layer in operable contact with the cathode. The electrolyte layer can be free of lithium phosphorus oxynitride. The method can further comprise the step of applying an anode layer in operable contact with the electrolyte layer in the case of solid state thin film batteries, or providing an anode that is wetted by a liquid electrolyte. Suitable anode materials include, but are not limited to, lithium metal, graphitic carbon, silicon, tin, as well as oxides and oxynitrides of these and other metals.

A method of operating a battery, includes the steps of providing a lithium ion battery comprising an anode, a cathode, and an electrolyte layer between the anode and the cathode. The cathode comprises a lithium, manganese, nickel, and oxygen containing compound. The electrolyte is free of lithium phosphorus oxynitride. A protective layer is disposed between the cathode layer and the electrolyte. The protective layer comprises lithium phosphorus oxynitride. The method further includes the step of operating the battery at elevated operating conditions comprising at least one selected from the group consisting of a temperature of at least 50° C. and a voltage of at least 4.5 V. The battery can be operated at a temperature of between 50° C. and 80° C. The battery can be operated at a voltage of between 4.5 V and 5.4 V.

The Lipon protective layer can further comprise at least one dopant which enhances electronic transport in the protective layer. The dopant can be at least one selected from the group consisting of transition metal elements, such as Ti, Fe, Ni, V, Cr, Cu, and Co. The dopant can be provided at a concentration of between 1% to 50% of the P mole content.

Lipon films doped with Ti and Fe are effective coatings. With Ti or Fe or another transition metal doping the thickness of the Lipon film can be increased. This is because the dopant increases the electronic conductivity so that contact can be established between the particles and current collector for a thick coating.

A lithium ion battery includes an anode, a cathode, and an electrolyte disposed between the anode and the cathode. A protective layer is disposed between the cathode and the electrolyte. The protective layer comprises lithium phosphorus oxynitride which in one embodiment can be essentially pure, and in another embodiment can comprise at least one electronic transport enhancing dopant. The dopant can be at least one selected from the group consisting of Ti, Fe, Ni, V, Cr, Cu, and Co. The dopant can be provided at a concentration of from 1% to 100% of the P mole content, and in another embodiment can be provided at a concentration of from 25% to 50% of the P mole content. The cathode can comprise a lithium, manganese, nickel and oxygen containing compound.

A method of operating a battery includes the steps of providing a lithium ion battery comprising an anode, a cathode, and an electrolyte disposed between the anode and the cathode. The electrolyte can be free of lithium phosphorus oxynitride. A protective layer is disposed between the cathode layer and the electrolyte. The protective layer comprises lithium phosphorus oxynitride and at least one electronic transport enhancing dopant. The method further includes the step of operating the battery at elevated operating conditions comprising at least one selected from the group consisting of a temperature of at least 50° C. and a voltage of at least 4.5 V. The battery can be operated at a temperature of between 50° C. and 80° C. The battery can be operated at a voltage of between 4.5 V and 5.4 V. The dopant can be at least one selected from the group consisting of Ti, Fe, Ni, V, Cr, Cu, and Co. The dopant can be provided at a concentration of from 1% to 100% of the P content, and in another embodiment can be provided at a concentration of from 25% to 50%. The cathode can comprise a lithium, manganese, nickel and oxygen containing compound.

Example Metal Doping on Lithium Phosphorus Oxynitride (Lipon) Electrolytes.

RF-magnetron sputtering was used to apply a Lipon coating with a dopant to a cathode material. The target was 2 inch diameter Li₃PO₄ and the sputtering power was 80 W (110V). The sputtering distance was 5 cm. The dopant was added to the target by mixing in metal or oxide powder, adding metal foil pieces or strips to the top surface, or co-sputtering with a separate (second) target in addition to the Li₃PO₄ target. The sputtering time was 0.5, 2 and 6 hours. The cathode material was LiMn_(1.5)Ni_(0.5)O₄ (MNO) (nGimat Co.) The BET surface area was ˜8 m2/g, and the pore volume was ˜0.05 cc/g.

Bond structures of metal-doped Lipon All metal-doped Lipon films had Lipon bond structures. N—O bond vibrations were observed in FTIR spectra. Based on XPS spectra, Fe (or Ti) may bond with oxygen. Coated and uncoated MNO particles had similar morphologies. Increasing the deposition time increased the amounts of phosphorus indicating thicker layers.

Cell Preparation

A CR2023 coin cell was prepared utilizing the resulting material Cathode: MNO:C:PVDF=80:10:10 wt % MNO/Celgard in 1.2 LiPF₆EC/EMC (1:1 v/v)/Li anode

Cycling performance was similar at constant C-rate. The capacity retention @ 5C was greater for Fe-Lipon-coated MNO than for other MNO samples. The cycling performance at 60° C. was better for coated MNO samples than for uncoated MNO sample. The capacity retention @ 5C was better for Fe-Lipon-coated MNO than for Ti-Lipon-coated and Lipon-coated MNO, which were better than uncoated MNO.

FIG. 1 is a plot of discharge capacity (mAh/g) with cycle number. Lipon coatings improve capacity at room temperature and 60° C. Capacity retention is based on 1st discharge capacity. The Lipon-coated MNO at 25° C. had a capacity retention after 50 cycles of 94.3%.

FIG. 2 is a plot of discharge potential (V) vs. capacity (mAh/g) for Lipon-coated MNO. FIG. 3 is a plot of discharge potential (V) vs. capacity (mAh/g) for bare MNO. Both results are at room temperature.

FIG. 4 is a plot of discharge potential (V) vs. capacity (mAh/g) for Lipon-coated MNO cycled at 60° C. FIG. 5 is a plot of discharge potential (V) vs. capacity (mAh/g) for bare MNO cycled at 60° C.

FIG. 6 is a plot of discharge capacity vs. cycle number at various C-rates, cycled at 25° C. There is negligible capacity reduction at increasing C-rates.

FIG. 7 is a plot of capacity/mAhg⁻¹ vs. cycle number for Lipon coated Li-rich MNC at differing C-rates. FIG. 8 is a plot of voltage (V) vs. Li/Li⁺ vs capacity (mAhg⁻¹) at different C-rates. A 220 mAh/g at a rate of 1C is achieved.

FIG. 9 is a comparison of discharge capacity datas of conventional and 1 h LIPON (3D) coated on Li-rich NMC composite electrodes at various rates in EC-DMC 1:2/LiPF₆ 1.2 M solutions (at 25° C.). FIG. 10 is a comparison of discharge capacity datas of 1 h and 3h LIPON (3D) coated on Li-rich NMC composite electrodes at various rates in EC-DMC 1:2/LiPF₆ 1.2 M solutions (at 25° C.).

FIG. 11 is a plot of voltage (V) vs. Li/Li⁺ vs capacity (mAhg⁻¹) for Lipon-coated Li-rich MNC for a 1^(st) cycle charge and a first cycle discharge.

FIG. 12 is an SEM of uncoated LiMn_(1.5)Ni_(0.5)O₄. FIG. 13 is an SEM of Lipon-coated LiMn_(1.5)Ni_(0.5)O₄ after a 0.5 hr deposition. FIG. 14 is an SEM of Fe-Lipon-coated LiMn_(1.5)Ni_(0.5)O₄ after a 2 hr deposition. FIG. 15 is an SEM of Ti-Lipon-coated LiMn_(1.5)Ni_(0.5)O₄ after a 2 hr deposition. There is no morphological difference between the MNO samples.

FIG. 16 is a plot of discharge capacity (mAh/g) vs. cycle number for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at room temperature.

FIG. 17 is a plot of potential (V) vs. capacity (mAh/g) for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at room temperature.

FIG. 18 is a plot of discharge capacity (mAh/g) vs. cycle number for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at 60° C.

FIG. 19 is a plot of potential (V) vs. capacity (mAh/g) for uncoated MNO, Lipon-coated MNO, Fe-Lipon-coated MNO, and Ti-Lipon-coated MNO, cycled at 60° C.

The foregoing description of the preferred embodiments of the invention has been presented for purposes of illustration. The invention is not limited to the embodiments disclosed. Modifications and variations to the disclosed embodiments are possible and within the scope of the invention. 

1.-19. (canceled)
 20. A method of making a cathode for a lithium ion battery, comprising the steps of: providing a cathode material comprising a lithium, manganese, nickel and oxygen containing compound; providing a lithium phosphate target; sputtering the lithium phosphorus oxynitride in a nitrogen plasma to coat the lithium, manganese, nickel and oxygen containing compound with at least a 1 nm coating of lithium phosphorus oxynitride.
 21. The method of claim 20, wherein the sputtering is RF magnetron sputtering.
 22. The method of claim 20, wherein the cathode material is provided as particles.
 23. The method of claim 22, further comprising the step of agitating or flowing the particles during the sputtering step.
 24. The method of claim 20, further comprising the step of applying a lithium salt electrolyte layer in operable contact with the cathode, the electrolyte layer being free of lithium phosphorus oxynitride.
 25. The method of claim 24, further comprising the step of applying an anode layer in operable contact with the electrolyte layer. 26.-40. (canceled)
 41. The method of claim 25, wherein the protective layer comprising lithium phosphorus oxynitride, and the protective layer is provided as a uniform coating from 0.5 to 10 nm on all sides of the of the particles prior to the electrode preparation, the coated particles being unannealed; the battery having capacity retention at 60° C.
 42. A method of making protected, free-flowing cathode material for a lithium ion battery operable at an upper voltage of 4.5 Volts vs. Li/Li₊ or higher, comprising the steps of: a) providing a cathode material comprising a lithium, manganese and oxygen containing compound as dry, free-flowing particles; b) providing precursor sources suitable for the vapor deposition of lithium phosphorous oxynitride; c) vapor depositing a uniform lithium phosphorus oxynitride protective layer of 0.5 to 10 nm onto said particles; wherein said protected, free-flowing cathode material remains dry and suitable for use as a cathode material without annealing.
 43. The method of claim 42, wherein the cathode material further comprises nickel.
 44. The method of claim 43, wherein the cathode material comprises Li[Ni_(x)Mn_(2-x)]O₄, where x is 0.5±0.1.
 45. The method of claim 43, wherein the cathode compound comprises LiMn_(1.5)Ni_(0.5)O₄.
 46. The method of claim 43, wherein the cathode material further comprises cobalt.
 47. The method of claim 46, wherein the cathode material comprises Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1.
 48. The method of claim 42, wherein the cathode material comprises particles comprised of Li_(1+x)Mn_(2-y)O₄, where x and y are independently 0 to 0.2.
 49. The method of claim 48, wherein the cathode material also comprises particles comprised of Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1.
 50. The method of claim 42, wherein the cathode compound comprises xLi₂MnO₃.(1-x)LiMO₂, where M is at least one selected from the group consisting of Mn, Co, and Ni, and x is 0.2-0.7.
 51. The method of claim 42, further comprising the step of agitating or flowing the particles during the vapor deposition step.
 52. The method of claim 42, wherein the lithium phosphorous oxynitride layer is produced using a plasma precursor source.
 53. The method of claim 42, wherein the vapor deposition is a sputtering process.
 54. A method of making protected, free-flowing cathode material for a lithium ion battery operable at an upper voltage of 4.5 Volts vs. Li/Li₊ or higher, comprising the steps of: a) providing a cathode material comprising a lithium, manganese and oxygen containing compound as dry, free-flowing particles; b) providing precursor sources suitable for the vapor deposition of lithium phosphorous oxynitride; c) providing at least one additional dopant precursor source suitable for the vapor deposition of Ti, Fe, Ni, V, Cr, Cu or Co d) vapor depositing a uniform, doped lithium phosphorus oxynitride protective layer onto said particles; wherein the dopant to phosphorous ratio ranges from 1% to 100%, and wherein the protected cathode material particles remain dry and suitable for use as a cathode material without annealing.
 55. The method of claim 54, wherein the cathode compound comprises xLi₂MnO₃.(1-x)LiMO₂, where M is at least one selected from the group consisting of Mn, Co, and Ni, and x is 0.2-0.7.
 56. The method of claim 54, wherein the cathode material comprises one or more compounds selected from i) Li_(1+x)Mn_(2-y)O₄, where x and y are independently 0 to 0.2; ii) Li[Ni_(x)Mn_(2-x)]O₄, where x is 0.5±0.1; iii) Li_(1+w)[Mn_(x)Ni_(y)Co_(z)]O₂, where w+x+y+z=1 and iv) Li[Mn_(x)Ni_(y)Co_(z)]O₂, where x+y+z=1.
 57. A free-flowing cathode material protected with a lithium phosphorous oxynitride layer produced using the vapor deposition method of claim
 42. 58. An electrode produced using the material of claim 57, further comprising the steps of: e) mixing said material with a binder and conductive additives to make a slurry; f) casting said slurry onto a current collector; g) drying said cast slurry to form said electrode, and h) optionally pressing or calendaring said electrode.
 59. A free-flowing cathode material protected with a doped lithium phosphorous oxynitride layer produced using the vapor deposition method of claim
 54. 60. An electrode produced using the material of claim 59, further comprising the steps of: e) mixing said material with a binder and conductive additives to make a slurry; f) casting said slurry onto a current collector; g) drying said cast slurry to form said electrode, and h) optionally pressing or calendaring said electrode. 